EP1224344B1 - Method and device for regulating the composition of solution(s) - Google Patents
Method and device for regulating the composition of solution(s) Download PDFInfo
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- EP1224344B1 EP1224344B1 EP00978961A EP00978961A EP1224344B1 EP 1224344 B1 EP1224344 B1 EP 1224344B1 EP 00978961 A EP00978961 A EP 00978961A EP 00978961 A EP00978961 A EP 00978961A EP 1224344 B1 EP1224344 B1 EP 1224344B1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
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- the invention relates to a control method the composition of solution (s) in the manufacture of cellulosic moldings, in which one (a) cellulose and a mixes water-containing amine oxide to form a suspension, (b) a cellulose solution from the suspension with water evaporation forms, (c) the cellulose solution through an air gap in extruding a precipitation bath containing an aqueous amine oxide solution, and there coagulated into shaped bodies, (d) through the shaped bodies an aqueous washing solution conducts in the remaining amine oxide the moldings are washed out, and (e) aqueous amine oxide solutions from stages (c) and / or (d) after concentration in returns step (a), which is a non-optical property of the solutions measured and based on the measured values the composition of the solutions are regulated.
- the invention also relates to a device for carrying it out this method with one equipped with dosing elements Mashing device, one connected to the mashing device Dissolving and evaporation device, one to the dissolving and evaporation device extrusion device connected via a line with a subsequent precipitation bath, at least one Wash bath containing a highly dilute aqueous amine oxide solution, and devices for measuring a property of the solution (s) to monitor their composition. Under the property of Cellulose solution is also intended in the context of the present invention a measurable physical behavior of the solution.
- the properties of those produced by the amine oxide process cellulosic moldings, especially the textile-physical ones Properties of the spun fibers and filaments depend on a high level Dimensions depend on the composition of the extrusion solution. To comply with optimal properties, it is therefore desirable the composition monitor the solution and keep fluctuations within narrow limits. In a continuous process such as the present amine oxide process is process monitoring for an economical driving style significant. It is therefore important to include the concentrations of the aqueous amine oxide solutions in steps (c), (d) and (e) measure and regulate the solution compositions.
- EP 0 254 803 discloses a method for producing an aqueous, pure N-methylmorpholine-N-oxide solution by reacting Methylmorpholine with an aqueous hydrogen peroxide, whereby one Mixtures of methylmorpholine distilled with water Methylmorpholine-water azeotrope at temperatures from 60 ° to 100 ° C reacted with an aqueous hydrogen peroxide solution and the Reaction solution then to the desired content of N-methylmorpholine-N-oxide focused on.
- the concentration of that The end product obtained can be obtained using the refractive index or a Density measurements are monitored, with the end product being only light is colored yellow and can hardly be detected as impurities Contain amounts of peroxide, methylmorpholine and carboxyl groups can.
- the present invention is based on the object Process for the production of cellulosic moldings according to the To create amine oxide process in which the composition of the Spinning solution can be monitored closely.
- the regulation of the composition should be done more precisely than this due to a refractive index range is possible.
- a method for Production of cellulosic moldings by the amine oxide process be created in which the compositions of the various Solutions occurring in the course of the process are then also regulated if the refractive index measurement is unusable, because the solutions absorb or scatter the light too much.
- a device for performing the method is also intended be created by changing the composition of solutions of the amine oxide process, both spinning solutions and also cellulose-free, aqueous amine oxide solutions within narrow limits can be held or eliminated.
- This task is carried out in the process mentioned at the beginning solved according to the invention in that a non-optical Property of at least one of the solutions mentioned and the Deviation (s) of the measured value or the measured values from a predetermined one Setpoint to regulate the composition (s) of this solution (s) used.
- measurement of the refractive index becomes a narrow tolerance range the measured variable. Deviations of the measured value from a certain setpoint immediately trigger an intervention on the Actuators of the control loop. It will therefore be stricter Regulation of the solution composition achieved than is possible if the control is only activated when the measured value reaches a predetermined value Leaves tolerance range.
- the non-optical property of the to be measured Solution is the dielectric constant, the (electrical) conductivity, the microwave intensity and speed, the density, the water content or the ultrasound speed.
- Transparent and opaque Solutions in the process can be measured using the same Property are monitored, reducing the measurement and control effort can be minimized.
- the water content can be determined according to Karl Fischer become.
- the preferred embodiment of the method is used to measure the temperature of the solution at or just before or after the measurement one of the solution properties mentioned and you compensate for that Measured value based on the measured temperature. Since the Temperature of the solution can vary, the measured values must be set to one Reference temperature can be converted at which the measured value of the concerned Property of the solution of target composition known with which the current measured value is to be compared.
- the reference temperature, to which the measured values are converted is, for example 50 ° C or 60 ° C.
- the property of the solution is preferably measured in-line.
- the in-line measurements not only allow a quick determination of the Solution composition with low flow resistance, but with spinning solutions, they also avoid this due to their fragility existing security risk, for example in Dead clearing of the line (e.g. sampling nozzle) by the possible There is an onset of run-away reactions.
- the dosage of the components in steps (a), (b) and (d) is used to regulate the solution composition. If, for example, a change in the composition of the spinning solution is found on the basis of the property measurement, an intervention in the dosage of the components pulp and / or solvent NMMO / H 2 O is necessary. To correct the composition of the precipitation bath solution, it may be necessary to intervene in the dosage of the washing solution flowing into the precipitation bath or to change the water dosage to the washing solution.
- stage (b) and / or stage (e) are used to regulate the solution composition. If the measurements show an undesirable shift in the ratio NMMO / H 2 O of the spinning solution, this can be corrected in stage (b) by throttling or increasing the water evaporation in this stage. Likewise, the concentration of the aqueous amine oxide solution to be returned to stage (a) can be regulated by intervening in the concentration or evaporation stage.
- the task is also in the device mentioned solved according to the invention in that in the line or a container, which contains the solution to be monitored, a device arranged to measure a non-optical property of the solution is, and that the measuring device upstream together with flow Dosing devices or evaporation devices Control loops for control the solution composition forms.
- the measuring device delivers one Measured value of the solution, e.g. their dielectric constant or Density leading to signals for the adjustment of actuators, such as e.g. the change in the speed of dosing devices or the Change in the heat output of the evaporators is formed.
- the measuring device comprises a device for measuring the Solution temperature and temperature compensation of that Measuring device delivered measured value.
- the measuring device already delivers temperature-compensated measured values, so that an immediate comparison with the given, related to a certain temperature Values of the solutions of target composition is possible.
- NMMO N-methylmorpholine-N-oxide
- the apparatus 2 can be a multi-wave apparatus as described in DE-C-198 37 210.8.
- the apparatus 2 is followed by a dissolving and evaporation device 3, in which the suspension of cellulose and NMMO / H 2 O formed in the apparatus 2 is converted into a solution by the application of heat and vacuum under water evaporation.
- a suitable method for this is known from DE-A-44 41 468.8.
- An extrusion tool 4 connects to the dissolving device 3 via a line 8, through which the spinning solution is extruded into a precipitation bath 5 via an air gap.
- a line 8 through which the spinning solution is extruded into a precipitation bath 5 via an air gap.
- fibers, filaments, foils or other shaped articles can be obtained.
- the molded body 6 thus obtained is fed to a washing stage 10 via a take-off element 7, in which residual amine oxide is washed out of the molded body 6.
- a measuring device 9 for measuring a non-optical property for example the dielectric constant or the density of the solution
- the measuring device 9 supplies a temperature-corrected signal to a microprocessor 12, which detects deviations from the target value of the solution and control signals via the signal line 13 to the dosing element 1 a for the pulp, the signal line 15 to the dosing element 1 b for the solvent mixture and the signal line 14 the dissolving and evaporation device 2 there.
- the washing solution is made the washing stage 10 is fed to the precipitation bath container 5 via a line 24.
- a measuring device 11 in this line provides the composition the used washing solution in line 24 and regulates this via the signal line 18 with the microprocessor 16 Valve 17 for adding water to washing stage 10.
- the used one Precipitation bath solution is through a line 19, which also cleaning devices (not shown) contains an evaporation stage 20 supplied in which the solution to a predetermined amine oxide concentration is evaporated.
- the concentration of the evaporated Solution is obtained by measuring a property using the measuring device 21 and actual-target comparison by the processor 22 into an actuating signal reshaped via the signal line 23 for setting the evaporation conditions the evaporation stage 20 is used.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Regelung der Zusammensetzung von Lösung(en) bei der Herstellung von cellulosischen Formkörpern, bei dem man (a) Zellstoff und ein wasserhaltiges Aminoxid unter Bildung einer Suspension mischt, (b) aus der Suspension unter Wasserverdampfung eine Celluloselösung bildet, (c) die Celluloselösung durch einen Luftspalt in ein Fällbad extrudiert, das eine wässrige Aminoxidlösung enthält, und dort zu Formkörpern koaguliert, (d) die Formkörper durch eine wässrige Waschlösung leitet, in der restliches Aminoxid aus den Formkörpern ausgewaschen wird, und (e) wässrige Aminoxidlösungen aus den Stufen (c) und/oder (d) nach Konzentrierung in die Stufe (a) zurückführt, wobei eine nicht optische Eigenschaft der Lösungen gemessen und aufgrund der Meßwerte die Zusammensetzung der Lösungen geregelt werden.The invention relates to a control method the composition of solution (s) in the manufacture of cellulosic moldings, in which one (a) cellulose and a mixes water-containing amine oxide to form a suspension, (b) a cellulose solution from the suspension with water evaporation forms, (c) the cellulose solution through an air gap in extruding a precipitation bath containing an aqueous amine oxide solution, and there coagulated into shaped bodies, (d) through the shaped bodies an aqueous washing solution conducts in the remaining amine oxide the moldings are washed out, and (e) aqueous amine oxide solutions from stages (c) and / or (d) after concentration in returns step (a), which is a non-optical property of the solutions measured and based on the measured values the composition of the solutions are regulated.
Die Erfindung betrifft auch eine Vorrichtung zur Durchführung dieses Verfahrens mit einem mit Dosierorganen bestückten Anmaischeapparat, einer an den Anmaischeapparat angeschlossenen Löse- und Eindampfungseinrichtung, einer an die Löse- und Eindampfungseinrichtung über eine Leitung angeschlossenen Extrusionseinrichtung mit einem nachgeschalteten Fällbad, wenigstens einem Waschbad, das eine stark verdünnte, wässrige Aminoxidlösung enthält, sowie Einrichtungen zur Messung einer Eigenschaft der Lösung(en) zwecks Überwachung ihrer Zusammensetzung. Unter die Eigenschaft der Celluloselösung soll im Rahmen der vorliegenden Erfindung auch ein messbares physikalisches Verhalten der Lösung fallen. The invention also relates to a device for carrying it out this method with one equipped with dosing elements Mashing device, one connected to the mashing device Dissolving and evaporation device, one to the dissolving and evaporation device extrusion device connected via a line with a subsequent precipitation bath, at least one Wash bath containing a highly dilute aqueous amine oxide solution, and devices for measuring a property of the solution (s) to monitor their composition. Under the property of Cellulose solution is also intended in the context of the present invention a measurable physical behavior of the solution.
Die Eigenschaften der nach dem Aminoxidverfahren hergestellten cellulosischen Formkörper, insbesondere die textilphysikalischen Eigenschaften der ersponnenen Fasern und Filamente hängen in hohem Maße von der Zusammensetzung der Extrusionslösung ab. Zur Einhaltung optimaler Eigenschaften ist es daher erwünscht, die Zusammensetzung der Lösung zu überwachen und Schwankungen in engen Grenzen zu halten. Bei einem kontinuierlichen Verfahren wie dem vorliegenden Aminoxidverfahren ist die Prozessüberwachung für eine wirtschaftliche Fahrweise von Bedeutung. Es ist daher wichtig, auch die Konzentrationen der wässrigen Aminoxidiösungen in den Stufen (c), (d) und (e) zu messen und die Lösungszusammensetzungen zu regeln.The properties of those produced by the amine oxide process cellulosic moldings, especially the textile-physical ones Properties of the spun fibers and filaments depend on a high level Dimensions depend on the composition of the extrusion solution. To comply with optimal properties, it is therefore desirable the composition monitor the solution and keep fluctuations within narrow limits. In a continuous process such as the present amine oxide process is process monitoring for an economical driving style significant. It is therefore important to include the concentrations of the aqueous amine oxide solutions in steps (c), (d) and (e) measure and regulate the solution compositions.
Aus WO 94/28212 ist es bekannt, von Zeit zu Zeit eine Probe der dem Extrusionsapparat zufließenden Spinnlösung zu entnehmen und ihren Brechungsindex zu messen. Dieser soll bei 60°C in dem Bereich von 1,489 bis 1,491 liegen, damit Extrusionsprodukte mit zufriedenstellenden Eigenschaften erhalten werden. Es ist ferner bekannt, den Brechungsindex der wässrigen Aminoxidlösungen innerhalb bestimmter Grenzen zu halten. So soll der Brechungsindex der wässrigen Aminoxidlösung für das Fällbad bei 60°C zwischen 1,3644 und 1,3708 liegen, während für die konzentrierte Aminoxidlösung für die Bildung der Zellstoffsuspension der Brechungsimdex in dem Bereich von 1,4620 bis 1,4628 liegen kann, ohne daß Dosierorgane betätigt oder die Verdampferbedingungen verändert werden müssen. Die Überwachung des Brechungsindex der Lösung in einem mehr oder weniger breiten Bereich erlaubt keine exakte Regelung der Zusammensetzung der Lösung. Außerdem versagt dieses Verfahren bei Lösungen mit starker Lichtabsorption und/oder -streuung.From WO 94/28212 it is known to take a sample from time to time the spinning solution flowing into the extrusion apparatus and measure their refractive index. This should be at 60 ° C in the Range from 1,489 to 1,491, so that extrusion products with satisfactory properties can be obtained. It is further known, the refractive index of the aqueous amine oxide solutions within certain limits. So the refractive index of the aqueous Amine oxide solution for the precipitation bath at 60 ° C between 1.3644 and 1.3708, while for the concentrated amine oxide solution for the formation of the pulp suspension of the refractive index in the area can be from 1.4620 to 1.4628 without metering elements operated or the evaporator conditions must be changed. Monitoring the refractive index of the solution in a more or less wide range does not allow exact regulation of the composition the solution. This method also fails in solutions with strong light absorption and / or scattering.
Die EP 0 254 803 offenbart ein Verfahren zur Herstellung einer wässrigen, reinen N-Methylmorpholin-N-Oxid-Lösung durch Umsetzung von Methylmorpholin mit einem wässrigen Wasserstoffperoxid, wobei man Mischungen von Methylmorpholin mit Wasser destilliert, das Methylmorpholin-Wasser-Azeotrop bei Temperaturen von 60° bis 100 °C mit einer wässrigen Wasserstoffperoxidlösung umsetzt und die Reaktionslösung anschließend auf den gewünschten Gehalt N-Methylmorpholin-N-Oxid auf konzentriert. Die Konzentration des so erhaltenen Entproduktes kann mit Hilfe des Brechungsindexes oder einer Dichtenmessung überwacht werden, wobei das Endprodukt nur leicht gelblich gefärbt ist und als Verunreinigungen kaum noch nachzuweisende Mengen an Peroxid, Methylmorpholin und Carboxylgruppen enthalten kann.EP 0 254 803 discloses a method for producing an aqueous, pure N-methylmorpholine-N-oxide solution by reacting Methylmorpholine with an aqueous hydrogen peroxide, whereby one Mixtures of methylmorpholine distilled with water Methylmorpholine-water azeotrope at temperatures from 60 ° to 100 ° C reacted with an aqueous hydrogen peroxide solution and the Reaction solution then to the desired content of N-methylmorpholine-N-oxide focused on. The concentration of that The end product obtained can be obtained using the refractive index or a Density measurements are monitored, with the end product being only light is colored yellow and can hardly be detected as impurities Contain amounts of peroxide, methylmorpholine and carboxyl groups can.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von cellulosischen Formkörpern nach dem Aminoxidverfahren zu schaffen, bei dem die Zusammensetzung der Spinnlösung genau überwacht werden kann. Die Regelung der Zusammensetzung soll genauer erfolgen als dies aufgrund eines Brechungs-indexbereiches möglich ist. Darüber hinaus soll ein Verfahren zur Herstellung von cellulosischen Formkörpern nach dem Aminoxidverfahren geschaffen werden, bei dem die Zusammensetzung der Lösung mit möglichst geringer Verzögerung geregelt wird, damit auftretende Schwankungen in der Zusammensetzung in engen Grenzen gehalten werden können. Insbesondere soll auch ein Verfahren zur Herstellung cellulosischer Formkörper nach dem Aminoxidverfahren geschaffen werden, bei dem die Zusammensetzungen der verschiedenen im Verfahrensverlauf auftretenden Lösungen auch dann geregelt werden können, wenn die Brechungsindexmessung unbrauchbar ist, weil die Lösungen das Licht zu stark absorbieren oder streuen. Schließlich soll auch eine Vorrichtung zur Durchführung des Verfahrens geschaffen werden, durch die Änderungen der Zusammensetzung von Lösungen des Aminoxidverfahrens, und zwar sowohl Spinnlösungen als auch cellulosefreien, wässrigen Aminoxidlösungen in engen Grenzen gehalten oder eliminiert werden können. Weitere Vorteile der Erfindung ergeben sich aus der folgenden Beschreibung.The present invention is based on the object Process for the production of cellulosic moldings according to the To create amine oxide process in which the composition of the Spinning solution can be monitored closely. The regulation of the composition should be done more precisely than this due to a refractive index range is possible. It is also intended to be a procedure for the production of cellulosic moldings by the amine oxide process be created in which the composition of the Solution with the least possible delay is regulated so occurring fluctuations in the composition within narrow limits can be held. In particular, a method for Production of cellulosic moldings by the amine oxide process be created in which the compositions of the various Solutions occurring in the course of the process are then also regulated if the refractive index measurement is unusable, because the solutions absorb or scatter the light too much. Finally, a device for performing the method is also intended be created by changing the composition of solutions of the amine oxide process, both spinning solutions and also cellulose-free, aqueous amine oxide solutions within narrow limits can be held or eliminated. Further advantages of the invention result from the following description.
Diese Aufgabe wird bei dem eingangs genannten Verfahren erfindungsgemäß dadurch gelöst, daß man eine nicht-optische Eigenschaft wenigstens einer der genannten Lösungen mißt und die Abweichung(en) des Meßwerts bzw. der Meßwerte von einem vorgegebenen Sollwert zur Regelung der Zusammensetzung(en) dieser Lösung(en) benutzt. Anders als das oben genannte Verfahren mit Messung des Brechungsindexes wird erfindungsgemäß ein enger Toleranzbereich der Meßgröße vorgegeben. Abweichungen des Meßwertes von einem bestimmten Sollwert lösen unmittelbar einen Eingriff an den Stellgliedern des Regelkreises aus. Es wird daher eine striktere Regelung der Lösungszusammensetzung erreicht als sie möglich ist, wenn die Regelung erst aktiviert wird, wenn der Meßwert einen vorgegebenen Toleranzbereich verläßt. Die Messung einer nicht-optischen Eigenschaft der Lösungen setzt zudem nicht die Durchsichtigkeit der Lösungen für das Licht der benutzten Wellenlänge voraus. Daher können auch Spinnlösungen, die definierte Anteile an Zusatzstoffen, wie z.B. Titandioxid, Farb- oder Füllstoffe enthalten, und im Prozess anfallende Aminoxidlösungen, die durch Verunreinigungen stark gefärbt sind, überwacht und in Bezug auf ihre Konzentration geregelt werden.This task is carried out in the process mentioned at the beginning solved according to the invention in that a non-optical Property of at least one of the solutions mentioned and the Deviation (s) of the measured value or the measured values from a predetermined one Setpoint to regulate the composition (s) of this solution (s) used. Different from the above procedure with According to the invention, measurement of the refractive index becomes a narrow tolerance range the measured variable. Deviations of the measured value from a certain setpoint immediately trigger an intervention on the Actuators of the control loop. It will therefore be stricter Regulation of the solution composition achieved than is possible if the control is only activated when the measured value reaches a predetermined value Leaves tolerance range. The measurement of a non-optical The property of the solutions also does not set the transparency of solutions for light of the wavelength used. Therefore, spinning solutions, the defined proportions of additives, such as. Contain titanium dioxide, color or fillers, and in Process resulting amine oxide solutions caused by impurities are strongly colored, monitored and in terms of their concentration be managed.
Die zu messende nicht-optische Eigenschaft der Lösung ist die Dielektrizitätskonstante, die (elektrische) Leitfähigkeit, die Mikrowellenintensität und -geschwindigkeit, die Dichte, der Wassergehalt oder die Ultraschallgeschwindigkeit. Durchsichtige und undurchsichtige Lösungen im Prozess können mittels Messungen der gleichen Eigenschaft überwacht werden, wodurch der Meß- und Regelaufwand minimiert werden kann. Der Wassergehalt kann nach Karl-Fischer bestimmt werden.The non-optical property of the to be measured Solution is the dielectric constant, the (electrical) conductivity, the microwave intensity and speed, the density, the water content or the ultrasound speed. Transparent and opaque Solutions in the process can be measured using the same Property are monitored, reducing the measurement and control effort can be minimized. The water content can be determined according to Karl Fischer become.
Nach der bevorzugten Ausführungsform des Verfahrens mißt man die Temperatur der Lösung bei oder kurz vor oder nach der Messung einer der genannten Lösungseigenschaften und kompensiert man den Meßwert aufgrund der gemessenen Temperatur. Da die Temperatur der Lösung variieren kann, müssen die Meßwerte auf eine Bezugstemperatur umgerechnet werden, bei der der Meßwert der betreffenden Eigenschaft der Lösung von Soll-Zusammensetzung bekannt ist, mit dem der aktuelle Meßwert zu vergleichen ist. Die Bezugstemperatur, auf die die Meßwerte umgerechnet werden, ist beispielsweise 50°C oder 60°C.The preferred embodiment of the method is used to measure the temperature of the solution at or just before or after the measurement one of the solution properties mentioned and you compensate for that Measured value based on the measured temperature. Since the Temperature of the solution can vary, the measured values must be set to one Reference temperature can be converted at which the measured value of the concerned Property of the solution of target composition known with which the current measured value is to be compared. The reference temperature, to which the measured values are converted is, for example 50 ° C or 60 ° C.
Vorzugsweise mißt man die Eigenschaft der Lösung in-line. Die in-line-Messungen erlauben nicht nur eine schnelle Ermittlung der Lösungszusammensetzung bei geringem Strömungswiderstand, sondern sie vermeiden bei Spinnlösungen auch das durch die Zersetzlichkeit der Lösung bestehende Sicherheitsrisiko, das beispielsweise in Toträumen der Leitung (z.B. Probenahmestutzen) durch das mögliche Einsetzen von run-away-Reaktionen besteht. The property of the solution is preferably measured in-line. The in-line measurements not only allow a quick determination of the Solution composition with low flow resistance, but with spinning solutions, they also avoid this due to their fragility existing security risk, for example in Dead clearing of the line (e.g. sampling nozzle) by the possible There is an onset of run-away reactions.
Bei einer Ausführungsform des erfindungsgemäßen Verfahrens greift man zur Regelung der Lösungszusammensetzung in die Dosierung der Komponenten in Stufe (a), (b) bzw. (d) ein. Wird z.B. eine Änderung der Zusammensetzung der Spinnlösung aufgrund der Eigenschaftsmessung festgestellt, ist ein Eingriff in die Dosierung der Komponenten Zellstoff und/oder Lösungsmittel NMMO/H2O notwendig. Zur Korrektur der Zusammensetzung der Fällbadlösung kann es erforderlich werden, in die Dosierung der dem Fällbad zulaufenden Waschlösung einzugreifen oder die Wasserdosierung zur Waschlösung zu verändern.In one embodiment of the process according to the invention, the dosage of the components in steps (a), (b) and (d) is used to regulate the solution composition. If, for example, a change in the composition of the spinning solution is found on the basis of the property measurement, an intervention in the dosage of the components pulp and / or solvent NMMO / H 2 O is necessary. To correct the composition of the precipitation bath solution, it may be necessary to intervene in the dosage of the washing solution flowing into the precipitation bath or to change the water dosage to the washing solution.
Bei einer anderen Ausführungsform des Verfahrens greift man zur Regelung der Lösungszusammensetzung in die Betriebsbedingungen der Stufe (b) oder/und der Stufe (e) ein. Ergeben die Messungen eine unerwünschte Verschiebung des Verhältnisses NMMO/H2O der Spinnlösung, so kann dies in der Stufe (b) korrigiert werden, indem die Wasserverdampfung in dieser Stufe gedrosselt oder verstärkt wird. Ebenso kann die Konzentration der in die Stufe (a) zurückzuführenden wässrigen Aminoxidlösung durch Eingriff in die Konzentrierungs- bzw. Eindampfungsstufe geregelt werden.In another embodiment of the method, the operating conditions of stage (b) and / or stage (e) are used to regulate the solution composition. If the measurements show an undesirable shift in the ratio NMMO / H 2 O of the spinning solution, this can be corrected in stage (b) by throttling or increasing the water evaporation in this stage. Likewise, the concentration of the aqueous amine oxide solution to be returned to stage (a) can be regulated by intervening in the concentration or evaporation stage.
Die Aufgabe wird ferner bei der eingangs genannten Vorrichtung erfindungsgemäß dadurch gelöst, daß in der Leitung oder einem Behälter, die bzw. der die zu überwachende Lösung enthält, ein Gerät zur Messung einer nicht-optischen Eigenschaft der Lösung angeordnet ist, und daß das Meßgerät zusammen mit strömungsmäßig vorgeschalteten Dosierorganen oder Eindampfeinrichtungen Regelkreise zur Regelung der Lösungszusammensetzung bildet. Das Meßgerät liefert einen Meßwert der Lösung, wie z.B. ihre Dielektrizitätskonstante oder Dichte, der zu Signalen für die Verstellung von Stellorganen, wie z.B. der Änderung der Geschwindigkeit von Dosierorganen oder der Änderung der Wärmeleistung der Eindampfapparate umgeformt wird. The task is also in the device mentioned solved according to the invention in that in the line or a container, which contains the solution to be monitored, a device arranged to measure a non-optical property of the solution is, and that the measuring device upstream together with flow Dosing devices or evaporation devices Control loops for control the solution composition forms. The measuring device delivers one Measured value of the solution, e.g. their dielectric constant or Density leading to signals for the adjustment of actuators, such as e.g. the change in the speed of dosing devices or the Change in the heat output of the evaporators is formed.
Vorzugsweise umfaßt das Meßgerät ein Gerät zur Messung der Lösungstemperatur und eine Temperaturkompensation des von dem Meßgerät gelieferten Meßwerts. Das Meßgerät liefert dann schon temperaturkompensierte Meßwerte, so daß ein unmittelbarer Vergleich mit den vorgegebenen, auf eine bestimmte Temperatur bezogenen Werten der Lösungen von Soll-Zusammensetzung möglich ist.Preferably, the measuring device comprises a device for measuring the Solution temperature and temperature compensation of that Measuring device delivered measured value. The measuring device already delivers temperature-compensated measured values, so that an immediate comparison with the given, related to a certain temperature Values of the solutions of target composition is possible.
Die Erfindung wird nachfolgend an Hand der Zeichnung näher erläutert, die das schematische Fließbild einer Ausführungsform der erfindungsgemäßen Vorrichtung zeigt.The invention will now be described with reference to the drawing which explains the schematic flow diagram of an embodiment shows the device according to the invention.
Wasserhaltiger Zellstoff und ein Gemisch aus N-Methylmorpholin-N-oxid
(NMMO) und Wasser werden durch die Dosierorgane 1a bzw. 1b
in einen kontinuierlich arbeitenden Anmaischeapparat 2 eingespeist.
Der Apparat 2 kann ein Mehrwellenapparat sein, wie er in
DE-C-198 37 210.8 beschrieben ist. Dem Apparat 2 ist eine Löse- und
Eindampfungseinrichtung 3 nachgeschaltet, in der die in Apparat 2
gebildete Suspension aus Zellstoff und NMMO/H2O durch Wärmezufuhr
und Unterdruck unter Wasserverdampfung in eine Lösung überführt
wird. Ein geeignetes Verfahren hierzu ist aus DE-A-44 41 468.8
bekannt. An die Löseeinrichtung 3 schließt sich über eine Leitung 8
ein Extrusionswerkzeug 4 an, durch das die Spinnlösung über einen
Luftspalt in ein Fällbad 5 extrudiert wird. Je nach Art der Beschaffenheit
des Extrusionswerkzeugs und der folgenden Operationen können
Fasern, Filamente, Folien oder andere Formkörper erhalten werden.
Der so erhaltene Formkörper 6 wird über ein Abzugsorgan 7 einer
Waschstufe 10 zugeführt, in der restliches Aminoxid aus dem Formkörper
6 ausgewaschen wird.Water-containing pulp and a mixture of N-methylmorpholine-N-oxide (NMMO) and water are fed through the metering elements 1 a and 1 b into a continuously operating
Erfindungsgemäß ist in der Leitung 8 zwischen der Löseeinrichtung
3 und dem Extrusionswerkzeug 4 ein Meßgerät 9 zur Messung
einer nicht-optischen Eigenschaft, z.B. der Dielektrizitätskonstanten
oder der Dichte der Lösung installiert. Das Meßgerät 9 liefert
ein temperaturkorrigiertes Signal an einen Mikroprozessor 12, der
Abweichungen vom Sollwert der Lösung feststellt und Stellsignale
über die Signalleitung 13 an das Dosierorgan 1a für den Zellstoff,
die Signalleitung 15 an das Dosierorgan 1b für das Lösungsmittelgemisch
und die Signalleitung 14 an die Löse- und Eindampfungseinrichtung
2 gibt.According to the invention, a
Wie aus der Zeichnung ersichtlich, wird die Waschlösung aus
der Waschstufe 10 über eine Leitung 24 dem Fällbadbehälter 5 zugeführt.
Ein Meßgerät 11 in dieser Leitung stellt die Zusammensetzung
der verbrauchten Waschlösung in der Leitung 24 fest und
regelt über die Signalleitung 18 mit dem Mikroprozessor 16 das
Ventil 17 für die Wasserzugabe zur Waschstufe 10. Die verbrauchte
Fällbadlösung wird durch eine Leitung 19, die auch Reinigungseinrichtungen
(nicht dargestellt) enthält, einer Eindampfstufe 20
zugeführt, in der die Lösung auf eine vorgegebene Aminoxid-Konzentration
eingedampft wird. Die Konzentration der eingedampften
Lösung wird durch Messung einer Eigenschaft mittels des Meßgeräts
21 und Ist-Soll-Vergleich durch den Prozessor 22 in ein Stellsignal
umgeformt, das über die Signalleitung 23 zur Einstellung der Eindampfbedingungen
der Eindampfstufe 20 dient.As can be seen from the drawing, the washing solution is made
the
Claims (7)
- Process for controlling the composition of solution(s) for the manufacture of cellulosic shaped bodies, comprisingcharacterized in that,(a) mixing cellulose pulp and a water containing aminoxide with formation of a suspension,(b) forming a cellulose solution from the suspension by evaporation of water,(c) extruding the cellulose solution through an air gap into an precipitation bath, containing an aqueous aminoxide solution, and the cellulose solution coagulates there to form shaped bodies,(d) conducting the shaped bodies through an aqueous washing solution in which remaining aminoxide is washed out from the shaped bodies,(e) returning aqueous aminoxide solution from stage (c)and/or (d) after concentration to stage (a),in which a property of the solutions is measured and according to the measured value the composition of the solutions is controlled,
at least one non-optical property of one of the said solutions is measured and the deviation(s) from the measured value respectively values from a predetermined reference value is used for the regulation of the composition(s) of these solutions, in which the property of the solution is chosen from the relative permittivity, the inductive conductivity, microwave absorption, the density, the water content and the ultrasonic speed. - Process according to claim 1, characterized in that, the temperature of the solution is measured at or shortly before or after the measurement of the property and the measured value of the property is compensated on the basis of the measured temperature.
- Process according to claims 1 to 2, characterized in that, the property is measured in-line.
- Process according to claims 1 to 3, characterized in that, recourse is made to the regulation of the composition of the solution in the metering of the components in stage (a),(c) or (d).
- Process according to claims 1 to 4, characterized in that, recourse is made to the operating conditions in stage (b) and /or (e) for the regulation of the composition of the solutions.
- Device for carrying out the process according to any of the claims 1 to 5, with a pulping device (2) equipped with metering elements (1a, 1b),
the pulping device (2) connected to a dissolving and evaporation device (3),
an extrusion device (4) connected via line (8) to the dissolving and evaporation device (3), with a downstream precipitation bath (5),
at least one washing bath, containing a diluted aqueous aminoxide solution, and
devices for the measurement of a property of the solution(s) to control their composition,
characterized in that, that in the line (8, 19, 24) or in a container, containing the solution to be controlled, a device (9, 21, 11) for the measurement of a non-optical property of the solution is arranged, and that the measuring device together with upstream metering elements (1a, 1b; 17) or evaporation devices (3; 20) forms regulating circuits (13, 14, 15; 18; 23) for the regulation of the composition of the solution. - Device according to claim 6, characterized in that, the measuring device (9, 11, 21) comprises a device for measuring the temperature of the solution and a temperature compensation of the measured value of the measuring device.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19947908 | 1999-10-06 | ||
| DE19947908 | 1999-10-06 | ||
| DE19949727A DE19949727B4 (en) | 1999-10-06 | 1999-10-15 | Method and device for controlling the composition of solution (s) |
| DE19949727 | 1999-10-15 | ||
| PCT/DE2000/003409 WO2001025512A2 (en) | 1999-10-06 | 2000-09-29 | Method and device for regulating the composition of solution(s) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1224344A2 EP1224344A2 (en) | 2002-07-24 |
| EP1224344B1 true EP1224344B1 (en) | 2004-11-17 |
Family
ID=26055177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00978961A Expired - Lifetime EP1224344B1 (en) | 1999-10-06 | 2000-09-29 | Method and device for regulating the composition of solution(s) |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6972101B1 (en) |
| EP (1) | EP1224344B1 (en) |
| CN (1) | CN1172034C (en) |
| AT (1) | ATE282727T1 (en) |
| AU (1) | AU1645701A (en) |
| WO (1) | WO2001025512A2 (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2777160A (en) * | 1952-12-13 | 1957-01-15 | Celanese Corp | Control system, wet spinning process and apparatus |
| DE3618352A1 (en) * | 1986-05-31 | 1987-12-03 | Huels Chemische Werke Ag | METHOD FOR PRODUCING AQUEOUS N-METHYLMORPHOLIN-N-OXIDE SOLUTIONS |
| US4996490A (en) | 1986-11-18 | 1991-02-26 | Atlantic Richfield Company | Microwave apparatus and method for measuring fluid mixtures |
| GB2217848B (en) | 1988-04-28 | 1991-11-27 | British Nuclear Fuels Plc | Monitoring the chemical composition of a fluid |
| US5354524A (en) * | 1993-05-24 | 1994-10-11 | Alan Sellars | Monitoring concentration of dope in product manufacture |
| DE4411815A1 (en) | 1994-04-07 | 1995-10-12 | Albatros Applied Technologies | Method for measuring a multi-component and / or multi-phase flowing medium |
| DE4437684C2 (en) | 1994-10-21 | 2001-07-26 | Friedrich Erasme | Device for measuring the concentration of a liquid that changes over time in a container |
| DE19509291A1 (en) | 1995-03-15 | 1996-09-19 | Akzo Nobel Nv | Measurement of cellulose@ concn. in soln. of tert. amine-N-oxide |
| DE19704609C2 (en) | 1997-02-07 | 2002-01-10 | Rossendorf Forschzent | Arrangement for measuring the local electrical conductivity in fluids |
-
2000
- 2000-09-29 WO PCT/DE2000/003409 patent/WO2001025512A2/en active IP Right Grant
- 2000-09-29 EP EP00978961A patent/EP1224344B1/en not_active Expired - Lifetime
- 2000-09-29 CN CNB008137714A patent/CN1172034C/en not_active Expired - Fee Related
- 2000-09-29 AU AU16457/01A patent/AU1645701A/en not_active Abandoned
- 2000-09-29 US US10/089,143 patent/US6972101B1/en not_active Expired - Fee Related
- 2000-09-29 AT AT00978961T patent/ATE282727T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP1224344A2 (en) | 2002-07-24 |
| WO2001025512A2 (en) | 2001-04-12 |
| WO2001025512A3 (en) | 2001-08-30 |
| ATE282727T1 (en) | 2004-12-15 |
| AU1645701A (en) | 2001-05-10 |
| CN1377429A (en) | 2002-10-30 |
| US6972101B1 (en) | 2005-12-06 |
| CN1172034C (en) | 2004-10-20 |
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